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Analytical Chemistry Division 2014

The Analytical Chemistry Division conducts research in a wide range of topics such as batteries, labs-on-chips, forensics, explosives detection, and better body armor. We utilize a variety of instruments, including scanning probe instruments, and focus on areas such as electrochemistry, organic compounds, separation and detection methods, and solar simulator projects.

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Analytical Chemistry Division 2014

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  1. Analytical Chemistry Division 2014

  2. Analytical Chemistry • Not JUST titrations! • We’re doing research in topics as diverse as better batteries, labs-on-chips, forensics, explosives detection and degradation, and better body armor. • We use almost every instrument you’ve seen plus some. • Two of the departments’ scanning probe instruments are in the Analytical Division.

  3. Analytical Chemistry Members • CDR Rob Calhoun • Professor Graham Cheek • Professor Christine Copper • Professor Judith Hartman • Associate Professor Dianne LuningPrak • Professor Dan O’Sullivan • Professor Maria Schroeder • Associate Professor Ron Siefert • Professor Paul Trulove

  4. RESEARCH INTERESTSProf. G. CheekMi 144 36625 Electrochemistry of organic compounds 1. Effect of Lewis acids on reaction pathways 2. Bio-electrochemistry of amino acids 3. Kolbe reaction RCOO- - 1 e- RCOO. RCOO. → R. + CO2 2 R. → R2 Solvents : Ionic liquids, water, acetonitrile Forensic Applications 1. Soil Characterization : X-Ray Fluorescence 2. Paper / Ink Characterization : Raman Spectroscopy

  5. RESEARCH INTERESTS Prof. G. Cheek Effect of Lewis acids on organic reactions Use of NMR, UV-VIS ? + Yb(TfO)3 Ionic liquid BMPY TfO Bio-electrochemistry of amino acids also dipeptides ? - 2 e- cystine - 2 H+ cysteine

  6. Development of Separation and Detection Methods for Environmentally Important Molecules Prof Christine Copperccopper@usna.eduMichelson 265project will also include collaboration with scientists at the Naval Research Laboratory, Washington, D.C. or at Drexel University

  7. Capillary Electrophoresis (CE) • CE was first used in the early 1980’s. • Reasonably high sensitivity (ppm or ppb) • Short separation time (<5 min) • Small Sample Volume (nanoliters) • Can be done on a microchip device instead of in a column *Separation is achieved based on different rates of migration of charged species in an applied electric field.

  8. Instrumentation CE instrument is in MI 264. This automated instrument can run samples when you are not there!

  9. Capillary Electrophoresis can be used to detect… • Explosives in seawater • Poisons in beverages • Ozone in submarine atmospheres • Nerve agents in atmospheres • Polyaromatic hydrocarbons in environmental samples • Carbon monoxide poisoning in blood • Illicit drugs in urine Current students: Micala Migneault and Clay Aronica

  10. Assoc. Prof. Dianne Luning Prak (prak@usna.edu) & Prof. Paul Trulove July 19-20, 2012 demonstration successfully evaluated the performance of “drop in replacement” advanced biofuel [50-50 mixtures of biofuel (made from used cooking oil and algae) and petroleum-based marine diesel or aviation fuel. ] http://greenfleet.dodlive.mil/energy/great-green-fleet/Midn 1/C Sarah Alexandre Fuel certification program/Office of Naval Research Goal: Analysis and testing of alternative fuels: density, viscosity, surface tension, speed of sound, bulk modulus, flash point, enthalpy of combustion (bomb calorimetry) Luning Prak, D. J., Alexandre, S. M., Cowart, J. S., Trulove, P.C., “Density, Viscosity, Speed of Sound, Bulk Modulus, Surface Tension, and Flash Point of Binary Mixtures of N-Dodecane with 2,2,4,6,6-Pentamethylheptane or 2,2,4,4,6,8,8-Heptamethylnonane” submitted to J. Chem. Eng. Data, 1/14

  11. Photolysis of munitions constituents Unexploded Ordnance in shallow waters How does the photolysis behavior of munitions constituents in marine systems differ from that in fresh water systems? ·salinity ·nitrate ·dissolved organic matter http://www.SERDP.org Midn 1/C James Breuer SUNSHINE LAB Solar Simulator Project involves ·preparing solutions ·using solar simulator ·analyzing samples with HPLC ·identifying products solid-phase extraction, LC/MS HPLC with autosampler Luning Prak, D.J., Milewski, E.A., Jedlicka, E.E., Kersey, A.J., O’Sullivan, D.W., 2013, “Influence of pH, Temperature, Salinity, and Dissolved Organic Matter on the Photolysis of 2,4-dinitrotoluene and 2,6-dinitrotoluene in Seawater,” Marine Chemistry, 157, 233-241.

  12. Harold Edgerton, photographer Professor Schroeder’s Research Interests • Improved Polymer Coatings for: • Military Transport (Humvees) • Body Armor • Hazardous Material Transport (DTRA) • Transparent Armor (ARL) • Laboratory Development: • Experiments in support of Chemistry of • Cooking course • Experiments for the IL courses Projectile hitting elastomer at > 500 mph

  13. Motivation for Coatings Research

  14. Continuing Student Project (DTRA) Protective Coatings for Hazardous Material Transport Current Research Student 1/C Philip Solt North Dakota Dec 31, 2013 Train Derailment – Lac-Megantic, Quebec 74 train cars containing crude oil 42 persons killed, 30 buildings destroyed July 6, 2013 Research Collaboration: Naval Research Laboratory (NRL) Defense Threat Reduction Agency (DTRA)

  15. Ron SiefertAssociate Professor3-6336 (office), Mi-243 (office), Mi-240 (lab) • Current Projects / Development of Nanoporous Sorbent Materials • Novel Sorbents (PMOs: periodic mesoporousorganisilicas) • For Analysis of Nitroenergetics (i.e, explosives) • For Analysis of Perchlorates (used as propellants) • As a substrate for catalysts to destroy contaminants Vehicle NH3 Emissions • Past • Projects Agricultural NH3 Emissions Measurements in the Chesapeake Bay Iron in Marine Aerosols Deposition of Nutrients to Surface Waters

  16. NanoporousPhotocatalysts for Decontamination of Nerve Agents Enhanced Detection of Explosives and Related Compounds OBJECTIVE: Develop organosilicas as sorbents applicable to the preconcentration of nitroenergetics and perchlorates for enhancement of in situ detection techniques APPROACH: Characterize the binding characteristics (e.g., selectivity, capacity, kinetics) of imprinted PMOs for nitroenergetics and perchlorate propellants. Use of HPLC and IC. Lab on a Chip Microfluidic devices using electro-osmotic flow.

  17. Natural Fiber Welding - Ionic Liquid Facilitated Biopolymer Mobilization and Reorganization Prof. Paul C. Trulove, MI248, trulove@usna.edu, 3-6622 Natural materials with dramatically enhanced physical and chemical properties • Current Impact • Producing natural materials with dramatically enhanced mechanical properties • Enabling tuneable natural material properties with high spatial resolution • Facilitating the integration of functional solid materials with electrical, magnetic and optical properties into natural fiber matrices • Natural Polymers • Natural polymers are renewable materials that have many attractive properties. Some natural silks have strength and toughness comparable to the best synthetic polymers. • The ability to modify and tailor the shape and properties of natural polymers is limited. QUANTITATIVE IMPACT STATUS QUO CH3COO− • MAIN ACHIEVEMENTS • Investigated the impact co-solvent properties on the natural fiber welding process • Demonstrated Inkjet printing of ionic liquids on natural fiber substrates • Utilized Laser heating to spatially control the welding of natural fiber substrates • Developed a continuous fiber welding process to coat yarns with functional solid materials • Evaluated the electrochemical and knitting properties of yarn based supercapacitors • Studied incorporation of fire retardant materials in natural yarns via fiber welding Research Goals Develop multi-functional natural materials and coatings with unique electronic, optical, and sensing properties for Air Force and DoD relevant applications in areas such as ballistic protection, energy storage, microelectronics, stealth, laser eye protection, optical computing, chem./bio sensing, in-situ medical applications • Ionic Liquids Solvents • We have shown that ionic liquids are powerful solvents for the dissolution and processing of a wide variety of natural polymers. • The solvating ability of ionic liquids provides a powerful tool for the modification and processing of natural polymers. END-OF-PHASE GOAL NEW INSIGHTS

  18. Control of Natural Fiber Welding Using Inkjet Printing of Ionic Liquids piezoelectric inkjet thermal inkjet Yellow – Rhodamine/IonicLiquid Green– Substrate Movies Obtained from Wikipedia http://en.wikipedia.org/wiki/Micro_Piezo

  19. Laser Induced Natural Fiber Welding Laser AFOSR Ionic Liquid Natural Fiber Substrate Use a Laser to Spatially Control the Welding of Ionic Liquid Coated Cotton Paper • CNC 40 W CO2 laser with raster and/or vector operation by Full Spectrum Laser (www.fslaser.com)

  20. Use of Ionic Liquids to Fabricate Biopolymer Composite Materials Bamboo (0.54 mg/cm) • Knitted Electrochemical Capacitors for Smart Textiles* Before Treatment After Treatment *Collaboration with Drexel University

  21. Knitted Linen/Bamboo/Viscose Capacitors! + + + Yarn Electrode VERY FLEXIBLE! Yarn Separator Yarn Electrode separator

  22. Questions?

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